Modified motor fuel and process of making same



Patented Feb. 3, 1942 MODIFIED Moron. FUEL AND raocsss or MAKING SAMESol Shappirio, Washington, D. C.

No Drawing. Application March 13, 1940,

Serial No. 323,840

8 Claims. (Cl. 44-9) This invention relates to motor fuels and tomethods of producing the same, and particularly to such motor fuelscontaining anti-oxidants, anti-knock ingredients, anti-gumming agents,dyes, etc., as well as processes of making the same, and particularlywher such modified motor fuels are produced from the motor fuel itselfby appropriate chemical or other treatments, whereby anti-oxidants,anti-knock ingredients, anti-gumminging agents, dyes, etc. are producedin situ in the motor fuel from ingredients in part, at least, presenttherein.

In the prior art there have been various suggestions for modifying motorfuels, particularly of the hydrocarbon type by the addition of agentsusually produced from extraneous sources for the particular purposes inhand, such as anti-knock derivatives or either the metallo ornon-metallo type, or anti-gum ingredients of various types, or dyes havebeen incorporated into such motor fuels for the purpose ofcharacteristically coloring them, such dyes having been producedextraneous of the motor fuel and added thereto. The separate productionof such added materials is both burdensome, undesirable and expensive.Thus, in the production of the metallo anti-knock compounds, of whichtetra ethyl lead is probably the best known and most widely used, theproduction of tetra ethyl lead outside of the motor fuel and itssubsequent incorporation therein, requires the manufacture and handlingof the very poisonous metallo organo derivative. Furthermore, one isthus limited to the use of individual, or at best a mixture of closelyrelated derivatives of one or two such compounds only, which are notalways found compatible with the ingredients of the motor fuel. Again,in connection with the addition of dyes to motor fuels in order to colorthe same, the dyes are the usual types of dyes produced outside of themotor fuel and incorporated thereinto. Difficulties have beenencountered in obtaining dyes that are compatible with the motor fuels,or preferably soluble therein. And the dyes available have been verylimited in character for this reason.

Among the objects of the present invention, therefore, is the productionof motor fuels or hydrocarbon derivatives utilizable for motor fuelpurposes, or for the production of motor fuels therefrom, in whichanti-oxidants, anti-knocking ingredients, anti-gumming agents, dyes,etc. are produced in the motor fuel or hydrocarbons, preferably fromingredients already present therein by appropriate chemical reactions.

Other objects include the production of such motor fuels or hydrocarbonmaterials containing novel components for anti-knock or anti-gum or dyepurposes, without necessarily being produced from the motor fuelsthemselves.

Other objects and advantages will appear from the more particulardescription given below, it being understood, however, that this moreparticular description is given by way of illustration and explanationonly, and not by way'of limitation, since modifications thereof may bemade by those skilled in the art without departing from the scope andspirit of the present invention.

The present application is concerned with the preparation of metalloorganic and other derivatives directly in the fuel or analogousmaterial, and preferably from constituents of the fuel or analogousmaterial itself without the addition of extraneous hydrocarbon sourcesis particularly emphasized, the oils of hydrocarbon character or theirderivatives or fractions or distillates being converted into compoundsin part, or to a limited extent, which upon further treatment arereadily converted into the metallo organo and other derivatives. Inaddition, extraneous substances, either for the purpose of forming themetallo organic substances within the fuel, or as a partial source forsuch metallo organic and other substances, some of the latter also beingderived from the fuel or analogous material, may also be added to thegasoline or other material treated.

The hydrocarbon materials treated may be the hydrocarbon oils, theirfractions and distillates including the gasolines, produced by variousprocesses and other hydrocarbon products that have fuel value. Suchgasolines, for example, may be those from straight distillationprocesses, from cracking processes either in the presence or absence ofair, from natural gas, etc. As pointed out, where the metallo organoderivatives are to be produced of the alkyl type, it is desirable tohave present in the gasolines or other hydrocarbon product, lowermembers of the paraflin series, and consequently gasolines containingsuch lower paraflins, such as ethane, propane and butane areparticularly desirable, but the gasolines containing aromatics also arereadily converted into the desired metallo organic compounds. Gasolinesand related materials produced during cracking or analogous heat andpressure treatment in the presence of air are highly advantageous, andmore particularly when in such processes the gasolines produced containeven a small amount of oxygen-containing substances, such as the others,since such oxygen-containing substances often act catalytically in theprocesses of converting some of the described intermediate substancesinto metallo organic compounds. The presence of such oxygen-containingcompounds as the aldehydes, ketones, etc. are desirable for otherpurposes set forth below.

If certain desired lower members of the paraffin series are not alreadypresent in the gasoline or other material to be treated, they may beadded to the same; and of course the same applies to other constituentsthat may be desired in the final products. Instead of converting theconstituents of the gasoline or analogous material directly into theintermediate that is to be converted into the metallo compounds, theremay be added to the gasoline or similar material, a substance which willbe converted into the metallo compound desired, the gasoline remainingsubstantially as it was before the conversion and the metallo compoundsbeing derived solely from the added substances, or any combination ofthese steps may be utilized.

Among the metals and non-metals that may be introduced into gasoline bythe processes there set forth, there may be mentioned lead, tin,silicon, antimony, arsenic, phosphorus, mercury, thallium, etc. Leadcompounds are particularly used for illustrative purposes therein inview of the wide use of lead compounds.

In the preparation of the metallo organic compounds in the fuel oranalogous material, the metallo organic compounds do not have to beseparately handled. The production of such metallo organic compounds inthe fuel and from fuel constituents may be carried out so that the fuelis present in a more limited quantity whereby a concentrated metalloorganic containing prodnot is obtained which may be secured bydistilling off the hydrocarbon products present, or which maysubsequently be diluted with more fuel or gasoline orrelated substanceto the concentration desired, or the metallo organic substance orsubstances may be prepared in the gasoline or analogous material in avery dilute condition, so that further dilution is unnecessary, and thespecial fuel is directly produced without more. The preparation of thedesired ingredients in very dilute condition is particularly desirablewhere some of the constitutents thus produced are not very soluble inthe motor fuels, although the very small quantities of such materialspres- 'ent needed for anti-knock, anti-oxidant, antigum, or dyepurposes, etc. do not require absolute solution, although in suchdilutions in which they are used, they are readily obtainable insolution form, or if necessary blending agents may be utilized toproduce the requisite solubility.

In many of the reactions of making metallo organic derivatives, thepresence of catalysts have been found to be highly desirable, suchcatalysts particularly referred to as Grignard catalysts areparticularly referred to, including for example, primary, secondary,tertiary amines, and their alkyl addition products, such amines beingaliphatic, aromatic or heterocyclic derivatives. Ex-

amples are aniline, dimethylaniline, carbazol, phenyl hydrazine,quinoline, etc. Other desirable catalysts or agents that may be presentinclude ether, ethers in general, ammonia and its derivatives, esters.These compounds may exist in the gasoline or other material undergoingtreatment, so the addition of such catalysts is not specificallynecessary. And this is particularly true in connection with thegasolines produced by oxidation processes, including ,both those of thevapor and liquid phase oxidation reactions.

' Other compounds, like the amines, etc. re-

ferred to above may be present in the gasoline by various methods, asindicated below, wherein they may be produced from constituents of thegasolines themselves, or may be introduced from external sources. Thecatalyst added may be selected from the named substances or otherderivatives, particularly with regard to their value in fuelcompositions, for example, the simpler ethers, and the amines,particularly the aromatic series thus being indicated.

Metallo organo derivatives as utilized herein may be produced in avariety of ways, as for example, by the methods disclosed in Patent No.2,012,356, granted August 27, 1935, entitled Metallo organo derivatives.

While in the production of Grignard reagents monohalogen derivatives areparticularly emphasized, where the halogen derivatives are convertedinto amines or other derivatives, higher halogen derivatives aredesirable leading to the production of diamines, etc., which diamines,particularly the aromatic diamines, like paraphenylenediamine, areparticularly valuable as in the production of dyes, etc.

The Grignard catalysts referred to above, such as the aromatic amines,like aniline and dimethylene, carbazol, etc., the aliphatic amines, likephenyl hydrazine, and the heterocyclic derivatives, like quinoline, willalso be present in the motor fuels, except as they may in part bealtered by the reactions to which the fuel fractions are subjected, andto the extent that they are present are desirable ingredients as antigumagents, etc.

It will be seen that in these reactions, metal is precipitated, whichmay be either magnesium or lead as illustrated above. Such precipitatedmetal formed by these chemical reactions is obviously in finely dividedcondition, and since they need not be removed from the fuel will lendtheir own anti-knock qualities to the motor fuel, particularly when usedin combination with the alkyl and aryl metallo derivatives.

4 While a number of metal derivatives may thus be introduced into thefuel by being made directly therein, if desired after the production ofone metallo organic compound, it may be converted partially or whollyinto other metallo compounds. And furthermore, if desired, instead ofthe Grignard intermediates produced as set forth above, or added to thefuel-for example, the Grignard reagents might be prepared in the usualmanner and then added to the gasoline or other fuel-the latter may beconverted into other derivatives than the metallo derivatives. TheGrignards are well known as excellent intermediates for the synthesis ofa number of organic compounds. So that they may be used as set forth inthe prior description to form a large number of organic compounds thathave value in fuels. For example, by appropriate treatments, they may beconverted into alcohols, phenols, aldehydes, ketones, etc. And thesereactions may be utilized so that a portion of the Grignard reagents areconverted into the metallo derivatives and a portion into other organiccompounds.

And further, many of the products may be made in the fuel from thehalides by taking crude hydrocarbon materials that must be subjected todistillation or other treatment, or treatments, in order to obtain motorfuels from them, by adding the requisite materials to them to form themetallo compounds, or converting a portion of such crude materials intocompounds that will form metallo derivatives, and then carrying out thedistillation or other treatments, so that a gasoline or analogousmaterial or fuel is obtained containing the metallo organic compoundsthat have been formed during the distillation or other treatment, whichmay or may not have been carried out under pressure.

Thus the introduction of the halogen to the material undergoingdistillation will yield halogenated fractions as, for example,halogenated motor fuel fractions which may accordingly be treated as setforth above. Or the introduction of halogen followed by contact of thehalogenated product with the sodium lead alloy, for example, beforedistillation, or at various stages thereof, will result in fractionssuch as motor fuels produced with the metallo derivatives in the fuelduring the distillation.

The Grignard reagents, as indicated above, are utilizable however inmany other directions for the production of both metallo derivativesother than those of the alkyl and aryl types strictly, and also for theproduction of many valuable ingredients in motor fuels which do notnecessarily contain any metallo component.

Thus. they may be utilized for the production of diazo compounds, bothof the aliphatic and aromatic series, and such diazo derivatives areimportant components in the motor fuels, whether or not they containmetallic derivatives, both varieties of which will be illustrated below,namely those containing metallo components, and those free from them.Diazo components are valuable in the motor fuels from two standpoints.Both because they have properties as anti-gum derivatives, and alsobecause they increase the power obtained from motor fuels. The contentsof such diazo compounds in motor fuel may be very low, not running morethan 1% in any event, and substantially smaller proportions, as low as.1% in the motor fuels giving markedly increased and valuable propertiesthereto. For example, derivatives of the diazo amino parafiins arereadily prepared, for which purpose the alkyl Grignard reagents may bereacted with the alkyl azldes, of which the following reaction isexemplary:

And as a result of which reaction there is produced compoundscorresponding with the magneslum salt of diazo amino methane. In theapplication of such reactions herein, there will usually be producedcomplex derivatives of such components, The magnesium derivativeproduced in accordance with the preceding method, may be permitted toremain in the motor fuel itself, or may be treated as a Grignard forother reactions, such as those to which the Grignards are capable,particularly as emphasized above. Thus various metallo derivatives maybe produced, such as the copper compound:

or other metallic derivatives, such as those of lead, etc. may similarlybe produced and utilized in the motor fuel, both because of the leadcomponent, and also because of the diazo grouping present. While thealkyl derivatives have been particularly referred to, diazo arylderivatives may be produced in an analogous way, and particularly diazoamino parafiins, and diazo amino aryls. And while such reactions and theproduction of such derivatives may be carried on outside of the motorfuel, and the diazo compounds or derivatives added to the motor fuel,desirably the compounds are produced within the motor fuel fromcomponents thereof, such as by halogenation, conversion into Grignardreagents, as set forth above, and then treatment with azides inaccordance with the preceding methods, and produced from the componentsof the motor fuels themselves result in complex derivatives thatdesirably flux each other, and remain in homogeneous combination withthe motor fuel constituents themselves. Further, as noted above ill inconnection with metallo derivatives generally, the reactions may becarried out utilizing the motor fuel as a diluting agent, so that thecompounds are produced in only smaller quantities, namely in the amountsin which they must be present in the final motor fuel, or the materialsmay be produced in the form of concentrates, and subsequently dilutedwith additions of motor fuel constituents to produce compositionscontaining the final minor quantities of such ingredients.

Similarly, the Grignard reagents may desirably be employed for theproduction of both metallo and non-metallo derivatives of the hydroxylamines. The hydroxyl amines, including hydroxylamine itself (OH.NH2) aredesirable ingredients in motor fuel compositions as antigumming agents.And these derivatives may accordingly be prepared from the motor fuelcomponents themselves, or if desired may be added to the motor fuel fromextraneous sources. Utilizing the Grignards for the production of thehydroxyl amine derivatives, the following is illustrative. The Grignardsproduced in the motor fuel in accordance with reactions set forth aboveare caused to react with nitrogen oxides. Thus ethyl magnesium iodide bythe action of nitric oxide is converted into derivatives of thebetadialkyl hydroxylamine type in accordance with the followingillustrative equation:

and such derivatives may be treated in various ways. They may bepermitted to remain in the motor fuel in that form without furthertreatment, or they may be converted into lead or other metallicderivatives as by reaction with the lead compounds, as set forth above,for the other Grignards, producing for example the lead compound:[(C2H5)2NO]2Pb. Or they may be decomposed with water to give thebeta-dialkyl hydroxylamine derivative. It will be noted that notrosoderivatives are produced, as set forth above, and such nitrosoderivativesare also important components of the motor fuel, in view oftheir anti-gum properties.

Nitroso beta-alkyl hydroxylamine derivatives may similarly be preparedby the action of nitric oxide on zinc ethyl and subsequent decompositionby water in accordance with the following equation:

/NO (IhCHzN As illustrative of the production of metallic derivatives ofsuch nitroso hydroxylamine derivatives, the following will also serve inaddition to that set forth above, wherein the alkyl Grignard is'reactedwith nitric oxide, and the resulting compound converted into metallicsalts, such as those of copper, lead, etc.:

2NO+CIiaMgI=CHiN ()Mgl the copper salt having the formula (CH3N2O2)2C\1and the lead salt the following formula (CHaNzOz) zPb reactions whenproduced in the motor fuels themselves result in complex mixtures ofsuch derivatives, and both alkyl and aryl derivatives may thus beobtained.

The production of diazo paraflin derivatives has been illustrated above,and reference may also be given to the production of diazo aryl salts byanalogous methods. For example, by the action of nitrous fumes on themetallo diaryl derivatives of which the following is exemplary:

And both of the produced components, and particularly the diazo salt,are valuable constituents of the motor fuel. The production of the diazosalt of the aryl type, for example, of course, have merely beenexemplified in the benzene diazo nitrate referred to above, and othertypes of derivatives, such as para-diazo-toluene nitrate may besimilarly produced, for example, from mercury para-ditolyl, while otheraryl derivatives of similar type may be produced, as well from themercury derivatives as the other metallo aryl derivatives.

The metallo aryl Grignard reagents may also be desirably employed in theproduction of azo compounds, for example, benzene magnesium iodideyielding with benzene diazonium chloride, azo benzene in accordance withthe following reaction.

Such azo compounds are desirable components in motor fuels, and thesetypes of reactions of which that illustrated is merely exemplary may beutilzed in the production of azo dyes in the motor fuels fromconstituents thereof, as more fully explained below. In this connectionit may be pointed out that the Grignard reagents are easily produced inthe motor fuel from constituents thereof as set forth above, and thediazo compounds may also be produced herein both by methods explainedabove and by subsequent methods, and such constituents produced in themotor fuel then permitted to react to produce the azo compounds.Substituted azo compounds of the true dye type may thus be produced inthe motor fuel. and in view of their production in complex mixtures insuch motor fuel from derivatives thereof, dyes can be produced in themotor fuel that remain in solution therein, which is dimcult in theproduction of many types of dyes by extraneous reactions, followed bytheir incorporation into motor fuels. Entirely new varieties of dyes incomplex mixtures are thus producible in the motor fuel from constituentsin this way. The Grignard reagents may be produced from the motor fuelsthemselves, and reacted withdiazo salts produced outside of the motorfuels, or as noted above, the diazo salts may also be produced in themotor fuels, or a portion thereof for reaction with the Grignardreagents. Or, as explained below, the diazo compounds may be producedfrom the motor fuel constituents themselves and reacted with Grignardreagents from external sources.

Other reactivities of the Grignard reagents may, of course, be utilizedto produce various types of organic derivatives, and are particularlyvaluable where complexmixtures are thus obtained because of theproduction of the Grignard reagents in situ in the motor fuels fromconstituents thereof. Thus the Grignard reagents absorb dry oxygen togive intermediate derivatives, which upon treatment with mineral acidsresult in alcohols or phenols, and when such reactions are employed inaccordance with the present invention complex mixtures of suchderivatives are produced in the motor fuels. The treatment with mineralacid may be carried out by agitating the hydrocarbon phase containingthe desired Grignard derivative with an aqueous mixture of mineral acid,such as hydrochloric acid, for example, until the desired reactionbetween the water and hydrocarbon phases is produced, or the hydrogenchloride may be dissolved or absorbed in alcohol, and the latterutilized in the reaction. Theprocesses may be formulated in accordancewith the following equations:

in which reactions R represents either alkyl or aryl, depending onwhether alcohols or phenols are produced.

Or the Grignards may be permitted to absorb carbon dioxide, andsubsequently treated with mineral acid in the manner set forthimmediately above to produce carboxylic acids, or their derivatives. Ifthe halogenation treatment prior to the production of the Grignardreagent is carried out on a gasoline which has first been aminized sothat amino aryls are present, these reactions may be utilized to produceamino benzoic acid and related compounds, particularly in complexmixture in the motor fuels produced in situ from constituents of themotor fuels themselves,

In carrying out such reactions as thosereferred to above, and as notedabove in connection halogenation of the gasoline fraction, for example,may be treated in situ with ammonia, preferably under pressure, orsodamide may be utilized to reactwith the chlorhydrocarbons to producethe amines. Other methods involve the nitration by nitric acid ormixtures of nitric and sulphuric acids applied to the gaoline fractionto produce nitro derivatives in the motor fuel itself, followed byreduction as by means of the usual reducing agent, such as powdered zincand acids to produce amino derivatives directly in the product.

The nitroparaillns instead of being directly reduced to the amines inthe manner set forth above, may be converted into the beta-alkyl oraryl-hydroxyl amines by reduction with stannous chloride, or with zincdust and water, or by electrolytic reductiom yielding various varietiesof the beta alkyl or aryl hydroxyl amines in the motor fuels themselves.

Reduction of the nitroso compounds derived through the Grignard andsimilar reactions as set forth above also yield amines. The presence ofamines in the motor fuel may be utilized very desirably for conversioninto other derivatives of great import in the motor fuel. This has beenin part indicated above by the production of various compounds includingthe diazo or diazonium salts. But once the motor fuel has been aminizedby any of the methods set forth above, or by other methods, as forexample, where phenols have been produced in the motor fuel by reactionsset forth above, such motor fuel containing phenols may be heated underpressure with ammonia, or preferably with the ammonium compound of zincchloride or of calcium chloride, naphthol, for example, in this wayyielding naphthylamines.

Other means of producing the amines particularly in cyclic and aromaticcompounds include the treatment of the halogenated gasoline fractionswith aluminum chloride by the Friedel and Crafts reaction to producecyclic and aromatic compounds. And these may then be heated withsodamide above 200, hydrogen being evolved, and the amines beingproduced. For example, heating naphthalene with sodamide above 200 C.yields alpha-naphthylamine.

The diazo salts or diazonium salts may be reduced to producephenylhydrazine derivatives and related compounds, and since this may bereadily carried out in the motor fuel itself from diazo compoundsproduced as noted above, these hydrazine derivatives are readilyproduced from components of the motor fuel in situ. Thus, for example,phenyl diazonium chloride reduced in this manner yields phenylhydrazinehydrochloride from which the base may be separated by washing withdilute alkalies. The process may be formulated in the followingreaction:

Once the amines have been produced in the motor fuel, or are presenttherein, and they may, of course, be added from extraneous sources forthis purpose, but desirably they are produced in complex mixture in themotor fuels themselves by any of the methods set forth above, they lendthemselves to a wide variety of treatments for the production of varioustypes of derivatives of great importance in the motor fuels, since theymay be readily converted into anti-gum components, dyes, etc.

One of the most important methods for deriv;

ing desirable components therefrom isby treatment with nitrous acid orits salts and esters. Under such treatments the aliphatic amines in thefue. ire converted into alcohols, which are, of themselves, importantcomponents of the motor fuel 1, -ixtures for various purposes, while thearomatic and cyclic amines are converted into diazo derivatives, whichlend themselves to various treatments, such as reduction, coupling, etc.

Various methods for producing such diazonium derivatives and alcohols bythe utilization of nitrous acid, its salts and esters are, of course,available. While diazotization is usually carried out at lowtemperatures in aqueous solution, it is not necessary that aqueoussolutions be employed, although they can be applied in manners analogousto that set forth above for other reactions involving the use of aqueoussolutions. For example, the motor fuel containing the aminizedderivatives may be agitated with the nitrous acid solution, whetherproduced from the salts or from the esters, so that the aqueous phase isin continuous contact with the hydrocarbon phase. And conversion of theamino derivatives is accordingly accomplished. In order to avoid loss ofdesirable products into the water phase, however, the reactions aredesirably carried out in non-aqueous media. The presence of the alcoholsformed by the action of the nitrous acid on the aliphatic amines isimportant in such reactions, since such alcohols act as a satisfactorymedium in which the diazotization may be carried out.

Thus absolute alcohol may be saturated with nitrous fumes, and thesaturated alcohol then added to the aminized motor fuel with theresulting production of diazo compounds. Other methods include theaddition of absolute alcohol or ether, if desired, but they are notessential to the aminized motor fuel, and then passing dry hydrogenchloride into such solution, heating to 40 or 50 until the last tracesof acid are removed.

The theoretical quantity of amylnitrite is then added, and this can evenbe done at ordinary temperatures, although lower temperatures areusually preferable in the production of diazo compounds, particularlywhere wide varieties of such diazo compounds are formed as is true inthe treatment of aminized motor fuels, some of the diazo compounds onlybeing stable at lower temperatures, as around 0. The diazo compounds arethus formed in the motor fuel fraction from components thereof.

It should be kept in mind, as pointed out above in connection with othertypes of compounds and methods, that it is not necessary to treat theentire fraction of gasoline in this manner, but only a portion thereofmay be subjected to such reactions, and after the production of thediazo compounds, such fractions added to the remaining portion of themotor fuel. Or the diazo compounds may be produced in concentratedcondition, and then diluted with the motor fuel constituents to producethe final fuel. The diazo compounds, while sometimes insoluble, willusually be found to be present in solution because of the complexderivatives obtained from the treatment of the motor fuels themselves,in which the various ingredients flux each other, and produce ahomogeneous composition. But where minor quantities of the diazocompounds in high dilution are utilized, the suspension of such diazocompounds in the motor fuel components also produce compositions thatmay be utilized directly.

Nitrosyl bromide and nitrosyl chloride, as well as nitro sulphonic acidmay also be employed for the production of the diazo compounds. Thus theaminized motor fuel, either with or without alcohols present, orintroduced for that purpose, has added thereto an alcoholic solution ofhydrogen chloride containing 2.5-3.0 mols of acid as compared with theamines present. The composition is cooled in ice, and a solution ofnitroso chloride, for example, in toluene added. The diazo salt is thusproduced.

The diazo salts may also be produced from the nitroso aryl hydrazinereferred to above by passing nitrous fumes into the solution of thenitroso aryl hydrazine. Quinone oxime present in the motor fuel bymethods of production that will follow from reactions given above, orintroduced into the motor fuel for that particular purpose may betreated with nitrogen trioxide, preferably in ethereal solution to yieldcorresponding diazo salts. Also by the action of chlorine or bromine onthe phenyl hydrazine derivatives produced in any of the methods setforth above will result in the production of diazo salts.

The reactions referred to above have particularly emphasized theproduction of the diazo salts and compounds of the aromatic and cyclictyp whereas examples of producing the diazo parafiins have also beengiven at an earlier portion of this specification. The hydrazines mayalso be utilized for producing diazo paraflins. Thus alkyl hydrazinesproduced in the motor fuel by any of the methods set forth above ontreatment with potassium pyrosulphate, followed by oxidation of theresulting compound with mercuric oxide yields diazo compounds. Thusethyl hydrazine treated with potassium hydrosulphate gives potassiumethyl hydrazine sulphonate, C2H5NHNHSO3K, which on treatment with themercuric oxide is converted into potassium diazo ethyl sulphonateC2H5N=N.SO3K.

The importance of the diazo compounds is readily recognized because oftheir various reactivities to produce different types of derivatives ofgreat importance in the modified motor fuels. Their reduction to producehydrazines has already beenindicated above, and such hydrazines arereadily methylated or alkylated as by the treatment with methyl iodideto produce alkyl hydrazine. The reduction of the diazonium salts to thehydrazines may, for example, be carried out by treatment with stannouschloride and hydrochloric acid, the aqueous phase being agitated withthe hydrocarbon phase containing the diazo salts until the desiredreduction is produced.

To briefly indicate some of the other important reactions of the diazocompounds, the following may be noted. If a motor fuel containing thediazo compounds are heated with absolute alco- 1101, they yieldhydrocarbons and aldehydes. Thus phenyl diazonium chloride heated withabsolute alcohol yields benzene on the one hand, and acetaldehyde on theother in accordance with the following equation:

And by such reactions aldehydes may bereadily produced in the motorfuel. If the motor fuel containing the diazo compounds are warmed andagitated with an aqueous solution, they yield phenols. Similarly warmedwith halogen acids, halogen derivatives are obtained. Phenyl diazoniumsulphate thus warmed with hydricdic acid yielding iodobenzene, nitrogenand acids. The various cuprous salts may be utilized in accordance withthe Sandmeyer reaction to produce corresponding derivatives. cyanideyields phenyl nitrile CcHsCN, and the nitriles, of course, uponreduction may be readily converted into amines. It is not intended bythese reactions to indicate that specific individual compounds are beingtreated, but these reactions exemplify the complex derivatives that areproducible in the motor fuels by these various treatments of the diazocompounds, complex mixtures of such derivatives, of course, beingobtained by these treatments, since the motor fuels contain variousdiazo derivatives of complex character.

The diazo compounds treated with hydroxyl amine result in amines. Thusdiazo benzene chloride yields aniline. And when treated with sulphurdioxide sulphazides are produced of which the following formulation issufficiently exemplary:

Such reactions may be carried out by agitating the hydrocarbon fractionscontaining the diazo compounds with aqueous solutionsof sulphur dioxide,the water removing the acids present.

It may be noted that the aryl hydrazines when treated with nitrous acidyield nitrosyl deriva-- tives, and the latter upon agitation with waterare converted into azide derivatives. Such reactions may be carried outby agitating the hydrocarbon fraction containing the phenylhydrazinewith the aqueous medium containing the nitrous acid, the processproceeding in accordance with the following reaction:

Thus the azides may be derived through the diazonium compounds, and thehydrazines, as wellas through the Grignard reagents, as stated earlier.

While the processes set forth above show the production of variousantioxidants, anti-gumming agents, etc. from constituents of the motorfuels themselves, the presence of various derivatives Thus cuproustherein, such as the amines. hydrazines, etc. lend themselves to theproduction of other types of anti-gumming constituents. Thus thesemi-carbazides may be produced from th hydrazine derivatives present bytreatment with potassium cyanide, the alkaline hydrazine sulphates beingheated with the potassium cyanide for this purpose. Or the alkylhydrazines treated with isocyanic acid or its esters results in thesecondary NH-- group receiving the carbarnide residue.

If the motor fuel fractions containing primary or secondary amines areheated with carbon disulphide, preferably in alhocolic solution, or inthe presence of alcohols formed in the motor fuels themselves, theresulting products heated to 110 yield dialkylated thioureas, thereactions being formulated as follows:

Urea derivatives may be produced by reaction of the aminized motor fuelfractions with phosgene or carbonyl chloride. Thus the aminizedfractions if itis desired to convert primary amines therein into theurea derivatives are desirably treated with carbonyl chloride attemperatures of 260270 C., but the secondary amines are more readilyconverted into the urea derivatives by action of the carbonyl chloride,or phosgene on the secondary amines in solution in the aminized motorfuel fractions.

Other types of anti-gumming derivatives, such as anthraquinone, arereadily produced in the motor fuels containing aromatics by the additionof phthalic anhydride' and aluminum chloride, the phthalic anhydridereacting with the benzol, for example, to give anthraquinone, whilehigher derivatives are produced from other homologues.

The various processes outlined above may be carried out by utilizing thereacting ingredients in their theoretical molecular equivalentproportions in accordance with the equations for the reactionsillustrated. Such molecular equivalent proportions being based on thecontent of the ingredient of th motor fuel which is to be utilized. Thuswhere chlorhydrocarbons are being reacted, the reactions may be based onthe use of the fraction containing the chlorhydrocarbons, utilizing anamount of such fraction which will yield the molecularly equivalentamount of chlorine. Similar considerations will apply to other reactionsinvolving the amines, etc.

The presence of various derivatives of the diazo and amino typesproduced in the motor fuel fractions is set forth above, and otherderivatives, such as the phenols, etc. lend such fractions desirably tothe production of dyes in the motor fuels themselves.

Thus amino-azo compounds may be produced by reaction of the diazoniumsalts with aromatic amines and their derivatives, phenyl diazoniumchloride yielding, for example, with dimethylaniline, dimethylanilineazobenzene in accordance with the following formulation:

This is exemplary of a wide variety of aminoazo compounds that can thusbe produced directly in the motor fuel. Of course, individual compoundsare thus not generally produced, since the diazonium compounds presentin the motor fuel by reactions as set forth above will be complexmixtures of such derivatives, and the result will be a heterogeneousmixture of derivatives; but the fiuxing action of such derivatives witheach other enables a homogeneous composition to be produced since onlysmall portions of the dye need be necessarily present in any event togive the gasoline the desired color. Such derivatives may be produced bypreparing the diazo compounds in the motor fuels themselves fromconstituents thereof, and adding the amines to react therewith fromextraneous sources, or the aromatic amines may be produced in the motorfuel, and the diazo salts produced extraneously thereof, or both sets ofcompounds may be pro- 7 duced directly in the motor fuel from componentsthereof, and the dye developed in situ in the motor fuel.

In a strictly analogous manner, the diazo compounds may be coupled withphenols, amino phenols, etc., amino sulphonic acids and otherderivatives usually coupled with such derivatives to produce amino azocompounds, or their derivatives.

Of course, such amino-azo derivatives may be further diazotized in themotor fuel, and coupled with further components to produce disazo dyes.As exemplary thereof, the following may be noted. A motor fuel fractioncontaining alphanaphthylamine is coupled with diazotized paraanisidineusing approximately a fraction of the motor fuel containing 30 parts ofalphanaphthylamine with approximately 25 parts of the diazotizedcompound. The resulting aminoazo derivative in the motor fuel is furtherdiazotized by agitation with an aqueous medium containing 11 parts ofhydrochloric acid and 15 parts of sodium nitrite for 1 hour at 10 C. Theaqueous phase is separated, and approximately 30 parts of beta-naphtholare added to the motor fuel fraction containing the diazo compounds, andcoupling takes place. If desired, however, to accelerat the coupling,the fraction containing the beta-naphthol and the diazo derivative maybe agitated with an aqueous medium containing approximately 9 parts ofcaustic soda, and approximately 2.0 parts of sodium carbonate in water,the temperature being maintained at about 5 C. A bluish red dye is thusproduced in solution in the gasoline fraction, directly therein, atleast in part produced from components of the motor fuel itself. Sincethe naphthylamine may be produced with the motor fuel itself, thebeta-naphthol may be produced in another portion of the motor fuel byreactions indicated above, and even the para-anisidine may be producedfrom a fraction of treated motor fuel by processes indicated above.Various derivatives of this type may be produced, so that a wide varietyof disazo dyes may thus be produced directly in the motor fuel itselffrom its components.

Or again, ortho-anisidine may be diazotized and coupled withbeta-naphthol to produce ortho-anisidine-azo-beta-naphthol as a dyecoloring the gasoline; and produced directly in the motor fuel byprocesses that will follow from those given above.

Dyes of the indophenol and indamine type may be readily produced in themotor fuel from components therein. The production of various amines andphenol derivatives from components of the motor fuels has been givenabove. Where the aromatic amines are present in the motor fuel, it maybe subjected to oxidation to produce the indamines therein, or phenolsmay first be added to produce the indophenol derivatives f mixed andsubjected to oxidation to produce tn desired indophenol or indamine, asthe case may be. Thus for motor fuel fractions containingpara-amido-dimethyl aniline and alphanaphthol, or nitrosodimethylanilineand alphanaphthol upon oxidation an indophenol is obtained. Thereactions may proceed at room temperatures, but elevated temperaturesmay be employed, as for example, above 100 F. in which event thereactions are-desirably carried out under pressure in order toavoid'loss of desirable lighter constituents from the motor fuel. Andthis observation, of course, applies to the various reactionshereinabove set forth where the elevated temperatures are employed, andwherein pressures are desirably maintained in order to avoid loss ofdesirable constituents in the motor fuel.

The phthalein dyes may be prepared, for example, from motor fuelfractions containing phenol desirably produced from constituents of themotor fuel in situ by methods set forth above, by condensation withphthalic anhydride, phenol itself thus yielding phenol phthalein. Otherphthalein derivatives may be prepared in an analogous manner.

The anthraquinone types of dyes are particularly important in the motorfuels, and may be readily produced therein from components of themotorfuel itself. The production of anthraquinone derivatives in themotor fuel has been illustrated above produced from components of themotor fuel itself. Such anthraquinone derivatives may be nitrated, andsubsequently reduced, utilizing the nitration and reduction reactionsillustrated above to produce amino anthraquinones which may then becoupled with the desirable ingredients, such as diazotizedpara-amino-toluene. In this way, for example, 1-methylamino-4-para-tolylamino-anthraquinone may be'produced yielding a blue dye coloring thegasoline blue.

The acridine dyestuffs may similarly be produced in the motor fuel insitu from components of the motor fuel itself. For example, the arylamines produced in the motor fuel may be condensed with benzaldehydefrom an extraneous source, or the-benzaldehyde may be produced in themotor fuel from constituents thereof, and the aryl amines introduced forthe condensation reaction, followed by treatment with hydrochloric acidto split off ammonia, the oxidation been set forth above, combinationsof those various methods may be employed to produce double substitutionsand various derivatives of organic character. For example, instead ofchlorinating or halogenating the motor fuel then halogenated to producechloramino derivatives in the motor fuel of both alkyl and arylcharacter, and such chloramino derivatives may thereuponbe utilized forany of the reactions set forth above, including conversion into metalloorganic derivatives having amino compounds bound in the moleculecontaining the metallo ingredient, or the Grignard reagents may beproduced from the halogen-amino derivatives, for example, and suchGrignard reagents reacted in accordance with the methods set forthabove. So that various combinations of the several processes set forthherein may be utilized. And as indicated in connection with severalindividual methods set forth above, one portion of the motor fuel may besubjected to one type of treatment for the production of a particularclass of derivatives, while another portion is subjected to a differenttreatment, and the two fractions then combined to have present bothtypes of derivatives, or successive operations of these methods may becarried out to produce both types of derivatives. Of course, it must bekept in mind that not only are complex mixtures of derivatives producedin all of these instances where the types of reaction products areproduced in the motor fuels themselves, and that where exemplaryreactions are given, they are merely exemplary of the type of compoundsbeing produced, since a number of derivatives in that class or type ofcompound will be produced by these reactions when carried out in situ,but complex combinations will, take place between various ingredients ofthe motor fuels themselves, where different organic derivatives arepresent.

Furthermore, while the methods set forth above have been particularlyillustrated in connection with their application to motor fuelfractions, those methods may be applied to petroleum oils or distillatesor fractions therefrom, whether are, therefore, desirably treated underpressure,

these methods may be carried out by taking the hydrocarbon materialsbefore distillation or other heat treatment to produce the motor fuelfractions, and incorporating the necessary reactants to produce theclasses of compounds desired, so that upon the distillation or heattreatment to produce the motor fuel itself, the methods are carried outfor producing simultaneousl the classes of compounds resulting from thereactions set forth. Similarly, a number of reactions as set forth aboveutilize reduction processes. In view of the wide use of hydrogenationmethods in the production of motor fuels today, as well as lubricants,etc., the reduction reactions may take place at the same time that thehydrogenation treatment is utilized for producing the hydrogenated motorfuels. For example, the ingredients necessary to produce the desiredclasses of compounds upon reduction may be present in the hydrocarbonmaterial before the hydrogenation treatment applied to the motor fuel,so that upon completion of the hydrogenation treatment, the reduction ofthe compounds present may be simultaneously carried out, thehydrogenated motor fuel derivatives being produced at the same time thatthe classes of compounds for anti-gum or other purposes are beingproduced in the motor fuel. Similarly, where refining treatments areemployed, involving treatments with caustic soda or sulphuric acid orsuccessive treatments of that character, and where, for example, an acidtreatment is necessary in connection with the production of particulartypes of compounds in accordance with the methods set forth above, theingredients necessary to produce the desired derivatives upon treatmentof sulphuric acid may be. introduced into the hydrocarbon materialsbefore the application of the sulphuric acid treatment,

for example, so that the refining with sulphuric acid is carried outsimultaneously with the treatment with acid necessary to produceanti-gum or other types of derivatives. These several examples willillustrate the application of ordinary refining methods as they arecarried out at the present time in the plant, and their utilization inproducing particular types of derivatives in the modified motor fuels inaccordance with the present methods, so that a single reaction of thatcharacter is sufficient to accomplish both ends.

While the invention has been particularly illustrated with motor fuelfractions such as gasoline, other hydrocarbon fractions and distillatesmay be similarly treated. For example, components, fractions ordistillates of the character known as lubricating oils and generally anyof the hydrocarbon fractions and distillates produced from petroleumderivatives having boiling points substantially higher than the motorfuel ranges, may be treated by any of the methods set forth above sothat such modified lubricating oils or other hydrocarbon fractions ordistillates may be modified in accordance with the various methods setforth above to produce new types of products containing the desiredderivatives either produced outside of such lubricating oil or otherhydrocarbon fraction or distillate and subsequently added thereto, ormore desirably produced in situ by the methods set forth above in suchlubricating oils or other hydrocarbon fractions or distillates.

Having thus set forth my invention, I claim:

1. A liquid hydrocarbon motor fuel containing a minor proportion of ametallo organo diazo compound.

2. A liquid hydrocarbon motor fuel containing a minor proportion of ametallo organo diazoarnino compound.

3. A liquid hydrocarbon motor fuel containing a minor proportion of ametallo organodiazo salt.

4. The process of producing modified motor fuels which comprisestreating a liquid hydrocarbon motor fuel to produce a metallo alkyltherein, and converting the latter at least in part to a metallo organodiazo derivative.

5. A liquid hydrocarbon motor fuel containing a minor proportion of acomponent selected from the group consisting of metallo organo diazocompounds, metallo organo diazo-amino compounds, and metallo organodiazo salts.

6. A liquid hydrocarbon motor fuel containing a minor proportion of ametallo organo diazo compound produced in situ from a component of thehydrocarbon motor'fuel.

7. A liquid hydrocarbon motor fuel containing a minor proportion of ametallo organo diazoamino compound produced in situ from a component ofthe hydrocarbon motor fuel.

8. The process of making modified motor fuels which comprises treating aliquid hydrocarbon motor fuel to produce a metallo alkyl therein, andconverting the latter at least in part to a metallo organo diazo-aminocompound.

SOL SHAPPIRIO.

